Refractory insulating brick and method of manufacture



Patented Oct. 7, 1952 PATENT OFFICE.

REFRAGTORYINSULATING BRICK 'AND' METHOD OF -'MANUFACTURE William L. stafiori somerville, :N. J assignor to J ohnsflIanvillenCorporation, New York, N. Y., a corporation oft-New .York

No Drawinga Application May 1'7, 1949; Serial-1N0. 93,844

12l3laims.., (01. ice--41) The; present invention is, a continuation'einei 5 partqof anduimproyement on,thatqdescribed-tinmy copending patent application, Serial ,No-.;-,.760-,-l 2fin; for. Refractory Insulating Brick and Methodi of Manufacture, filed J uly; 10,2 3,94%,- anew abandoned:

Many different .,molding, compositions and methods have been heretofore'proposed for the manufacture of light "weight refractory insulat inggbrick; Conventional methods generally, involved admixture of an organic burn out mate v rial [witha plastic clay-grogmix;;molding the,-;

mixture to shape, and drying and burningoutli" theorganic filler during firing of the shaped brick ;1 to develop porosity. Difficulty has b'een en countered in attempts to "develop refractory-1m sulatingbrickmof such low density asctoladapl them for efficient heat insulation, byzreascnzwoi themanufacturing problems encountered in (16:, veloping the necessary internal porositvwith-i out serious loss of compressive strength and yol=',.

umetric stability. The insulating bricks which are produced iby.aconventional-methodsstendrto develop an undesirable: degrees-pf 1- volume-sooner traction iand ispalling; as. well {as lossiof istren th'z when employed: as furnacewliningsz; exposedi temperatures:substantiallyrinxexcess aofwLZGQlF-f A primary: object otzthe; present-invention is;.tm provide: a refractory insulating-1 ricknof: tili ll weight which:resists;:spallinamnd-aexhibit v ume. stability atitemperatures asthi h-ras-Q0i Fm" Another: .obiectris tmprovideu a o1umeL-stablerlight weightnre'fractcry:insulating brick-channel; such ,compressivestrength and-resistance tether-,1 malashocle :asz tdqadaptaitt for; iusesin :lininQSrrfor high -;temperature;:iurnaces;

A iurtherzobject .tomprovide, an; eoonom-ical 40 iidefficientzmetnod; of; making:hightem erature insu1ating ,.bricko0fiuhighi q a y-,=

With :the: -;aboye objectsrinrviewriihe. invent on consistsyin, the improved; -,ref-raetoryinsulating brick and methodof manufacture which are-here 5 inafter; describedand:moresiparticularly defined-1. by, the accompanying;claims;

The present invention is hased upon the. (Ch-S7: covery that a, ,;refractory insulatingubrick. ci lighty weight and, of exceptionala volumetric stability; v

and compressive strength at high temperatures can be produced, byincorporatingfinely. divided metallic aluminum and alumina: in ,a .plastic clay; batch ,which-isrmolded, dried zandifiredlto iorm thebrickh: Satisfactory, bricks are obtainedywhen i 155;

2o. thebatch contains 2-5 dry Weight of metallic aluminum and 251-30% alumina, together with-a, good grade of kaolin clay and-grog of the same composition as. the brick. The bricks herein.

-referred to. are moldedand fired shapesi which may be of standard size or which may beaconsiderably larger, as for example withthe dimensions 24 x 9 x 2 inches,

An economical source bimetallic-aluminum:

- and alumina in suitable dry weight-proportions, is

a partially hydrated pulverulentaluminum dross. Howeven; many crude aluminum drosses contain. impurities of a kind and in amount having anadverse effect on the desired propertiesotthe finished ,brick.

Finely.:divided ,crude -.a1-mninum=v vdross reacts. violentlyzxwith hot water, with liberation of.-hy drogem gas and, ammonia"; and accordingly it 'is not'-rpracticable ,or desirable tozyincorporate the crude. .drcssmin 'more than minor proportions ,in weticlay mixtures which are to-be-molded,, dried andgfired, because rapid liberation of-gas de velops. fissures and cracks: throughout v the mold- GdlfihfiPBn. V

Dependable resultsioan-be obtained by incorpo-o rating. granularzaluminum and finely divided calcined alumina in a plastic olaybatch in approxi-v mately the proportions-indicated above. Astute able-form of granularealuminum is made..byblow-, inggwithau az-fine stream ofmolten aluminum .r so:;as-;:to' :produce rough metal pellets classifying as to standard screen size chiefly. between 10 and 28,1mesh.- An available source of alumina may be corundum or fused alumina c1assifying ,as.to.

size-between 40 and mesh. However, there-- iszsome advantage in employing alcalcinedelul-t mina,; or, a grog of high alumina to silica ratio, as the source of alumina, since such calcined alumina materials are porous and have comparatively' low density.

When partially prehydrated aluminum dross."- orla'mixture of granular aluminum and calcined alumina, is incorporated in a plastic "clay brie molding batch in suitable "proportions;- themold ed brick, after drying and firing to a high temperature, is; m'ore j refractory and volume-stable than brickjmadeoof a similarlyproportionedmix ture of refractory clay andxcommercial, corundumof equivalent aluminumoxide' and impurity oxidecontent. Corundum is exceedingly refractory; is inertfchemically, andfhas a lOWihGlHlaP-Gkr pansion when heated over the normal, firing-tem= peiaturev range..- I-Idwever, 'corundum" is insuf ficiently reactiver when admixed ;with ;plastic" re;

:iractory...clays.r.in,. the. theoretical proportions to enter into combining reactions with the silica of the clay at brick-firing temperature. Furthermore, the expansion rate of corundum in the proportions called for is insufficient to counterbalance the shrinkage of the clay, when firing a predetermined molded mixture to the temperatures required to develop optimum volumetric stability.

Sawdust or other organic filler material is embodied in the plastic molding batch as burn-out material for developing porosity. However, in following the procedure of incorporating partial- 1y hydrated aluminum dross or grained metallic aluminum in the batch, a substantially greater degree of porosity and much greater strength and volumetric stability is obtained in the fired product than would be expected from the composition of the batch. The amount of water which is added to the mixture for making up a batch is only sufficient to plasticize the mixture for shaping. However, during the drying and initial firing stages the molded batch also incorporates a substantial proportion of combined water, including the combined water present in the plastic clay binder, and also combined water which is present in the partially hydrated dross or as hydrated metallic aluminum. The increase in porosity of the resulting brick, which is developed without adverse effect on the strength and volume stability, is believed to be attributable to the gradual release of hydrogen and other gases resulting from liberation and decomposition of combined water during the final high temperature firing operation.

Suitable molding mixtures for producing insulating refractory bricks having a density in the range 60 to 67 lbs/cu. ft., a modulus of rupture of 125-200 lbs/sq. in., a compressive strength of 200-400 lbs/sq. in., and having high volumetric stability and resistance to spalling, have approximately the following dry weight composition: Kaolin 45-50%; calcined alumina 25-30%; metallic aluminum 2-5%; and grog 20-25%. Sawdust is introduced to the extent of about 8-12% of the mixture.

Molding mixtures in which aluminum dross is present, and which have proved effective for producing light weight insulating refractory bricks having exceptional volumetric stability at temperatures of 3000 F. or lower, and which resist spalling over long periods of use at such temperatures, are the following:

Per cent Sawdust 14-15 Kaolin 45-50 Aluminum dross 15-40 -20 Grog The sawdust preferably consists of white and yellow pine ground to a size of substantially --14 mesh. A preferred kaolin is one of uniform fine grain structure having a pyrometric cone end-point (PCE) of at least cone 33. A good grade of Georgia kaolin or washed Florida kaolin is satisfactory. A satisfactory aluminum dross comprises waste products from the refining of substantially pure metallic aluminum. The dross from heavily alloyed aluminum has been found to give unsatisfactory results. Certain alloying metals, for example magnesium and copper, adversely affect the insulation brick when present in substantial quantity. For example, as little as /2% of magnesia in a refractory insulation brick imparts high shrinkage characteristics when the brick is subjected to reheat firing at 3000" F. A satisfactory dross is one containing large amounts of aluminum oxide, substantial amounts of aluminum nitride and metallic aluminum, and small amounts of aluminum carbide and impurities. The grog is preferably made of burned brick of the same kind as that produced by the present process.

The aluminum dross reacts vigorously with hot water, evolving heat and gases. The first step in the process when using dross, consists in prereacting the aluminum dross with hot or cold water prior to its incorporation in the brick mix. This preliminary hydration reaction is necessary in order to precondition the dross to reduce its tendency for excessively rapid gas and heat liberation during the brick molding and drying operations. An incidental reason for this preliminary reaction is to minimize evolution of objectionable odors and combustible gases during drying operations.

A suitable dross, before hydration, had the following composition:

Per cent Aluminum oxide 51.80 Aluminum nitride 19.78 Aluminum metal 22.65 Magnesium oxide; 0.19 Copper oxide .01 Ferric oxide 1.55 Silica and other impurities 4.02

After partial hydration the dross had the following approximate analysis:

Combined water and other impurities 15.0

A suitable kaolin clay has the following composition:

Silica 53.7% Iron oxide 1.5% Alumina 44.9%

Preliminary treatment of the aluminum dross may include the steps of heating water to a temperature of about 200 F., then sprinkling pulverulent dross into the water in the proportions of about two pounds of dross to one pound of water. This amount of water is substantially that theoretically necessary to form aluminum hydrate by reaction with about one-fourth of the aluminum content of the dross. Evolution of ammonia and other gases starts almost immediately, and the reaction is continued at the indicated temperature for about two hours, at the end of which period the dross shows about 10% gain in dry weight and is considered to be in satisfactory condition for incorporation in the brick mix. partial hydrationand oxidation of some of the aluminum nitride, carbide and metallic alumimum in the dross produces a comparatively dry product by the end of a two hour reaction with water in the proportions indicated. Any residual water may be completely removed by air-drying the product of the reaction, and the dross is then conditioned for use in a brick batch by breaking up any soft lumps of reacted dross material.

A typical molding batch is one comprising 14% sawdust, 46.4% kaolin, 22.1% prehydrated aluminum dross and 17.5% grog. The grog is waste from grinding fired brick or the indicated com- The exothermic reaction and...

position to size.=. All *of the dry-ingredientsishouldr. besized to pass-a 35 mesh 'screen;..-and thezkaolin should be so finely divided as to all passcaAS-x mesh-screen.- The -batch=may be prepared. for molding by mixing the kaolin; sawdust. and gro The plastic tempered mixture which is thus. formed is loaded into molds of convenient .sizer After the molding operationithe: brick:shouldibe subjected to a slowi drying. operation. at .a temperatures of 200-400 R and -.the.-- dry -.bricksthenfired in an' oxidizin'g- -atmosphere' to a .final: temperatureof 2600 (pyrometric cone l6) In producing. the bricks usingla molding mix-h turecommune-2540a calcined aluminayand v 2-5% grained metallic alum-inum together with kaolin-and about 20-25 grog, it is not necessary ing the grained aluminum probably; develop a thin-oxide coating over each grain-whichserves to limit thewater reactivity of the metal to an; extent such that the final brick -product, ;afterfiring in an oxidizing atmospherefor: several hours at-a temperature in the neighborhood of 2600-2700 F.--andeventafter exposure to oxidizing furnace temperaturesof 3000 F: ion-several hours, still retains from about .5l701%f 0ffih81" divided metallic aluminum distributed -'through--' out the structure;

A typical molding batch expressed in'dry weight;

proportions, for producing a brick'of. abouti65 -6'T lbs/cu. it. density.and 200'lbs-./sq. inch transa v se stren th. wa a l ws;

Percent Calcin'edlalumina 28 Kaolin. 47. Grog; 22, Grained aluminum 3L 'li' k' ,a ter. Linear} rm age 81%.(approximate) Y Thermal' conductivityfig g; 3:60 "B. t. u. in./lir./sq.

Y ft. -12, meantemperature2000f *F. i PCE above cone 37 (3308 F.)

The linear shrinkage tests were supplemented by raisinga hot furnace. lining made. of the brick toatemperatureof,280091. within a period of l-ly ihours, holding the-temperatureconstant for aperiod of G-Lhours, and then allowing the furnace lining tocool overnight. This cycle was repeatedten times... Similarfurnaoe linings were subjectedto two to. five cycles of rapidly heatin to3000 F. andholdingsuch temperatur for 5-6 hours before coolingfover, nightQAt the end of such tests, the bricks'forming the furnacezlining werefound to. be .unmarred, uncracked and unbroken, and to' show only slight degrees of.shrink-' age at" the hot face ofthe brick. The, best available commercial grades of' refractory insulating brick cannot stand up under such severe tests without excessive*-shrinkage, cracking and spelling.

lic aluminum :sanm-alm-ina, in :comparison :cwith; bricks: made-from abatches lcontainingrinoz alumi-iz 1 v 5 num ritican beshown :that .4 during. the1process:of; ovenedryingathe, bricks. then firingzithemcinzam;

oxidizing atmosphere: at a;temperature ofzz255flfr F; for twor hours, then at 260.01 F.1for.=twentya-rouri; hours. the kaolin -content1of::the:brick; suffersz .aa i

weight loss '.of:;13 eawhereamthealuminumrcone.

tentaoi .tlielbrick showsa a weightaincrease average; ing .a21-'. /;j% based .on: .its original.rweightiprior z'toi1 hydration-a. The;weight:increaseathustexhibiteda; bytthea aluminum :suggestsithe reason forithea'exe-s L 1 ceptiona-llyihigh volumeistabilityxand low densities ofrtheibrick. Byipartial hydration; ofraluminums. dross the aluminum metaltandznitride arezpartialsz, lyzconverted to=aluminumr hydroxideonhydratee; andiduringithe ifiringin an? oxidizing atmosphere-1 zoncombined .water=:'is .slowly. liberated-i and zdecom to prehydrate-thealuminum.- The small amount of fine rained-aluminum present in-thisvmo1d'-- ing mixture is not excessively reactive with the water present in'the'batclir- Themethodof form posed: andiadditionali oxygen is absorbed tozcone vert tlieumetal-L to i aluminum; oxide: This a con-- versione takes =-place 1 in-la wayswhich insures thev presence of highly reactive metallic aluminum:

251m: substantial amount withinthe-batch at tem i peratures high'enough tobr ing-zabout direct com- 1 liming-reactions withsilicarin theclaya r The high temperature :refractory insulating brickherein described contain alumina and silica-'- r inapproximately" the 'weight ratio of 251 :or

65 70::35-=303 A firedrefractoryinsulation brick havinganalumina to silica ratio of about 2 :'1=im--- parted thereto "by incorporating 2718 aluminum 1 dross with 58.2% kaolin clay and'-l4 sawdust in=the--mo1ding mixture-developed less than-3 volume *shrinkage or expansion upon being sub jected to-'-a standard -reheat firingorshrinkage tESi?"8;t" 3000-F.- in theinanner heretofore de scribedl Thefired-brickanalyzed-603% -Si0z;

1.6% FezOa, 67.2% A1203 and small amounts or metallic aluminum and aluminum-nitride." Tests on an insulation brick having 1 an alumina to silica-ratio "of'2=: 1 imparted thereto by incorporating finely 1 divided corunduin with the-clay in" the moldingmixture, developed shrinkage to the ex tent -of 8 -12 "of the brick volumeon- -reheat-' firing-to 3000* FL- Thus insulation brick in Whicli= the alumina and silica content ranges between-65 and- 70% alumina to 3530 silica; made-"byincorporatingpartiallyhydtatedaluminumdross or metallic aluminum andcalcined alumina-inth'eclaymolding-mixture; exhibited much greater volume stability onrelieavfiring to 3000 as compared to-insulation-brickof the same alumina and'silica contentimparted'by-addition of finely divided corundum to the clay -molding-mixture;

The it present brick exhibit by X-ray powderpatterns a comparatively high contentof crystalline mullite: In fact; examination" of 'X-ray;

powder patterns has shown the presence of -a mullitecrystal'phaseginproportions greater'th'an would-be expectedifrom 'the'composition and heat treatment. The presence of mullite in this" pro portion helps: to explain thehigh-strength-and volumetric stabilityof the product, but-:is-veryunusual inan unvitrifiedprod'uct which'ha's not been exposed to the temperatures of fusion of" the principal alumina and'silica components of the product:- 1 The presence of mullite 'in suchhigh 7 propo'rtionsyis believed toresult from the particular procedure employed in the manufacturing operation.

Whenvfinely divided dross containing metallic aluminum or aluminum nitride (not more :than- 6% coarscr than standard -20-"meshscreen) is 7 preliminarily reacted with about half its weight of water in accordance with the present process, approximately half of the total metallic aluminum or aluminum nitride is converted to aluminum hydroxide, and this aluminum hydroxide forms a coating over the metallic and nitride 1 particles, which coating insulates and protects the particle cores from further reaction. The thus partially reacted metal or metal nitride is then incorporated in the plastic molding batch with additional .water, and no substantial further reaction with water takes place during the period in which the molded shape is dried to remove uncombined water. Decomposition of the aluminum hydroxide and oxidation of the uncombined metal and nitride takes place only gradually during the progressive stages of the firing treatment, and a substantial proportion of the metal retains its metallic form until firing temperatures in excess of 2000 F. are developed. At such temperatures the hydroxide coating of the metal particles has decomposed exposing the metallic aluminum to oxidation. The metal at these temperatures is at least partially in nascent state and so reactive that it is believed to enter into combination reactions not only with the oxygen of the surrounding atmosphere but also with the silica component of the clay binder. Substantial amounts of crystalline mullite result from this reaction, even though the reaction temperatures are several hundred degrees below those at which mullite is usually formed by fusion reactions between alumina and silica.

The invention which has been thus described by detailed example is not limited as to such details and it is to be understood that variations, changes and modifications are contemplated within the scope of the invention as defined by the following claims.

What I claim is:

1. A light weight refractory insulating brick having a density of 60-67 lbs./cu. ft. and substantial volumetric stability up to 3000 F. consisting essentially of A120: and SiO: in the weight ratio of about 2:1 and having a high content of crystalline mullite, said brick being an unvitrified oxidized and fired reaction product of a uniformly distributed mixture comprising water, finely divided kaolin clay, alumina, combustible material and metallic aluminum.

2. A refractory insulating brick having a density of 60-67 lbs/cu. ft. and volumetric stability up to 3000 F. comprising, the oxidized and fired reaction product of alumina, metallic aluminum and kaolin clay bonding agent, said brick consisting essentially of alumina and silica in approximate dry weight ratio proportions of 65-70z35-30, and having a high content of crystalline mullite.

3. A lightweight refractory insulating brick having a density of 60-67 lbs./cu. ft. and substantial volumetric stability at 3000" F., said brick comprising a fired product consisting essentially of alumina and silica in approximate dry weight proportions of 65-70 to 35-30 and containing distributed therethrough approximately .5-1% of finely divided metallic aluminum.

4. A refractory insulating brick having a specific gravity of approximately 1 and having a PCE above cone 30, comprising the oxidized and fired reaction product of a mixture comprising finely divided alumina, aluminum hydrate, metallic aluminum and refractory bonding clay, said brick consisting essentially of alumina and silica in approximately the weight proportions of 2:1, and having a high content of crystalline mullite.

5. A refractory insulating brick having a specific gravity of approximately 1 and having a PCE in the range of cones 34-38, a transverse strength of -200 lbs/sq. in., and a crushing strength of -400 lbs/sq. in., consisting essentially of A120: and $102 in the approximate weight ratio of 2:1 and having a high content ofcrystalline mullite, said brick being a substantially unvitrified fired product. I

6. In the manufacture of refractory brick the steps comprising, incorporating 2-5% dry weight of finely divided metallic aluminum in a plastic brick molding batch together with finely divided alumina, bonding clay and water, and molding and firing the resulting mixture to a temperature of at least about 2600 F.

7. In the manufacture of light weight refractor-y insulating brick the steps comprising, partially hydrating finely divided aluminum dross with water to react about half of the metal and nitride content to form a hydrate coating for the dross particles, and incorporating 15-40% by weight of said partially hydrated dross in a plastic brick molding batch comprising finely divided kaolin clay, water and an organic combustible material.

8. In the manufacture of porous insulating refractory brick of about 65 lbs/cu. ft. density consisting essentially of alumina and silica, in the weight proportion of about 2:1, the steps comprising, forming a plastic batch containing water and a uniformly distributed mixture of approximately 20-25% dry weight of finely divided grog, 45-50% finely divided kaolin having a PCE of at least 33, 25-30% alumina, and 2-5% metallic aluminum, adding 23-12% of the mixture of finely divided organic combustible material, charging the mold with said batch, drying the molded shape and heating it in an oxidizing atmosphere to burn out the organic content and firing to a temperature of at least 2600 F. for a time suflicient to develop dimensional stability.

9. In the manufacture of porous insulating refractory brick the steps comprising, forming a plastic batch containing water and a uniformly distributed mixture of 40-50% dry weight of finely divided kaolin having a PCE of at least 33, 2-5% finely divided metallic aluminum, 15-40% finely divided alumina and 8-15% of the mixture of finely divided organic combustible material. charging a mold with said batch, drying the molded shape, and heating it in an oxidizing atmosphere to burn out the organic content, and to a firing temperature of approximately 2600 F. to develop dimensional stability.

10. A process of making refractory insulating brick which comprises, reacting with approximately half its weight of water an aluminum dross consisting essentially of alumina, aluminum nitride and metallic aluminum, to partially convert the dross to aluminum hydrate, with liberation of ammonia and hydrogen, forming a molding batch containing approximately one part water and two parts dry solids comprising 15-40% by weight of said partially hydrated dross in dry pulverized form, 8-15% of sawdust, 0-20% grog and the balance chiefly finely pulverized refractory plastic bonding clay, molding said batch, drying the molded product, and firing it in an oxidizing atmosphere to a temperature of at least about 2600 F. v

11. In the manufacture of insulating refractory brick of approximately 65-67 lbs/cu. ft. density and 200 lbs/sq. in. transverse strength consisting essentially of alumina and silica in the weight proportions of about 2:1, the steps comprising, forming a plastic batch containing water and a uniformly distributed mixture of approximately 47% finely divided kaolin, 22% grog, 28% finely divided calcined alumina and 3% finely divided metallic aluminum, together with approximately 10% of the mixture of finely divided organic combustible material, charging a mold with said batch, drying the molded shape and heating it in an oxidizing atmosphere to burn out the organic content, and subjecting the 15 thus fired brick to a final firing temperature of 2600 F. to develop dimensional stability.

12. In the manufacture of refractory brick, the steps of molding a plastic brick composition comprising finely divided alumina, bonding clay, water, and from 1.8-5% dry weight of finely divided metallic aluminum, and firing said molded brick to a temperature 01 at least approximately 2600" F.

WILLIAM L. STAFFORD.

REFERENCES CITED The following references are of record in the file of this patent:

FOREIGN PATENTS Number Country Date 413,238 Great Britain 1934 587,595 Great Britain 1944 

1. A LIGHT WEIGHT REFRACTORY INSULATING BRICK HAVING A DENSITY OF 60-67 LBS/CU. FT. AND SUBSTANTIAL VOLUMETRIC STABILITY UP TO 3000* F. CONSISTING ESSENTIALLY OF AL2O3 AND SIO2 IN THE WEIGHT RATIO OF ABOUT 2:1 AND HAVING A HIGH CONTENT OF CRYSTALLINE MULLITE, SAID BRICK BEING AN UNVITRIFIED OXIDIZED AND FIRED REACTION PRODUCT OF A UNIFORMLY DISTRIBUTED MIXTURE COMPRISING WATER, FINELY DICIDED KAOLIN CLAY, ALUMINA, COMBUSTIBLE MATERIAL AND METALLIC ALUMINUM. 